Iron and lithium isotope systematics of the Hekla volcano,Iceland — Evidence for Fe isotope fractionation during magma differentiation

In this study potential iron isotope fractionation by magmatic processes in the Earth's crust was systematically investigated. High precision iron isotope analyses by MC-ICP-MS were performed on a suite of rock samples representative for the volcanic evolution of the Hekla volcano, Iceland. The whole series of Hekla's rocks results from several processes. (i) Basaltic magmas rise and induce partial melting of meta-basalts in the lower part of the Icelandic crust. The resulting dacitic magma evolves to rhyolitic composition through crystal fractionation. During this differentiation the δ^56/54Fe_IRMM-014 values increase successively from 0.051 ± 0.021‰ for the primitive dacites to 0.168 ± 0.021‰ for the rhyolites. This increase can be described by a Rayleigh fractionation model using a constant bulk fractionation factor between all mineral phases (M) and the silicate liquid (L) of Δ^56/54Fe_M–L = ? 0.1‰. (ii) The basaltic magma itself differentiates by crystal fractionation to basaltic andesite composition. No Fe isotope fractionation was found in this series. All basalts and basaltic andesites have an average δ^56/54Fe_IRMM-014 value of 0.062 ± 0.042‰ (2SD, n = 9), identical to mean terrestrial basaltic values reported in previous studies. This observation is consistent with the limited removal of iron from the remaining silicate melt through crystal fractionation and small mineral-melt Fe isotope fractionation factors expected at temperatures in excess of 1050 °C. (iii) Andesites are produced by mixing of basaltic andesite with dacitic melts. The iron isotope composition of the andesites is matching that of the basaltic andesites and the less evolved dacites, in agreement with a mixing process. In the Hekla volcanic suite Li concentrations are positively correlated with indicators of magma differentiation. All Hekla rocks have δ⁷Li values typical for the upper mantle and demonstrate the absence of resolvable Li isotope fractionation during crystal fractionation. As a fluid-mobile trace element, Li concentrations and isotopes are a potential tracer of magma/fluid interaction. At Hekla, Li concentrations and isotope compositions do not indicate any extensive fluid exsolution. Hence, the heavy Fe isotope composition of the dacites and rhyolites can be predominately attributed to fractional crystallisation. Iron isotope analyses on single samples from other Icelandic volcanoes (Torfajökull, Vestmannaeyjar) confirm heavy Fe isotope enrichment in evolving magmas. Our results suggest that the iron isotope composition of highly evolved crust can be slightly modified by magmatic processes.     

Metamorphic alteration,mineral paragenesis and geochemical re-equilibration of early Archean quartz–amphibole–pyroxene gneiss from Akilia,Southwest Greenland

Quartz–amphibole–pyroxene gneiss from the island of Akilia, Southwest Greenland has been claimed to contain the earliest traces of life on Earth in the form of biogenic carbonaceous matter encapsulated as inclusions in apatite crystals. Various lines of evidence, including petrography, geochronology, field relations, and geochemistry, have, however, been presented that challenge this interpretation. Textural relationships and geochemical signatures in this controversial gneiss presented here manifest a complex, spatially variable metamorphic history that includes granulite- and amphibolite-facies overprints and metasomatism. A peak metamorphic, granulite-facies, quartz–orthopyroxene–clinopyroxene–amphibole–magnetite assemblage is preserved in only a few centimeter-scale layers within the 5-m-thick, quartz–amphibole–pyroxene gneiss unit. Calcite veinlets that appear to postdate the peak metamorphism occur in pyroxene. The quartz–amphibole–pyroxene gneiss unit has subsequently experienced isochemical (except hydration) amphibolite-facies alteration during which pyroxenes were retrogressed to amphiboles and magnetite, and calcite was consumed. Parts of the quartz–amphibole–pyroxene gneiss that contain texturally late hornblende have experienced metasomatic alteration by Al-carrying fluids. These fluids controlled the alteration of pyroxenes and amphiboles to hornblende, and modified the trace-element composition by remobilizing LREE and Eu. Apatite has variable REE composition and ⁸⁷Sr/⁸⁶Sr in the quartz–amphibole–pyroxene gneiss, but on the local scale (cm) is in equilibrium with co-existing silicates. Effective recrystallization of apatite crystals as well as co-existing silicates during several stages of the metamorphic history makes the intact preservation of diagenetic apatite with encapsulated primary carbonaceous matter implausible. Hence, it is highly unlikely that Akilia apatite could serve as repository of the earliest traces of life on Earth.     

Zircon typology, geochronology and whole rock Sr–Nd isotope systematics of the Mecsek Mountain granitoids in the Tisia Terrane (Hungary)

Summary Zircon typology and ages together with petrological data suggest similarities in the origin of the K–Mg-rich granitoids of the Mecsek Mountains (Mórágy Unit, Tisia Terrane, S Hungary) and the durbachitic to K–Mg-rich rocks of the South and Central Bohemian Batholiths. Our investigations evidence a characteristic bimodal distribution of zircon types and ages. Zircons of normal magmatic habit and a typology around S24 show an age of 354±5Ma. Zircons of tabular habit of subtype S4 indicate a possibly younger age of 339±10Ma. The ages and typology of zircons from plutonic rocks in the Mecsek Mountains strongly resemble those from the Rastenberg granodiorite in the South Bohemian Batholith (Austria). This, as well as Rb/Sr and Sm/Nd isotope systematics, support the assumption of simultaneous formation and close spatial relationship between the Mecsek Mountain granitoids and the Rastenberg granodiorite. Thus, the Mecsek Mountains granitoids likely formed in a Late Palaeozoic palaeo-position S or SSW of the Rastenberg granodiorite. Having experienced a similar metamorphic and magmatic evolution during the Carboniferous, at least the northernmost part of the Tisia Terrane, the Mórágy Unit, is therefore considered to represent a former part of the Helvetic-Moldanubian zone.     

Rb‐Sr systematics of the Claret Creek Ring Complex and their bearing on the origin of upper Palaeozoic igneous rocks in northeast Queensland

The Claret Creek Ring Complex forms a minor part of the extensive Upper Palaeozoic calcalkaline province of northeast Queensland. Although the Claret Creek Ring Complex contains 10 mappable units, it was formed about 300 m.y. ago over a time interval no greater than 10 m.y. This interval is short compared with the overall duration of Upper Palaeozoic igneous activity, which lasted from approximately 320 m.y. to 270 m.y. in this area. Although geochemically distinct, the complex shares a common initial ⁸⁷Sr/⁸⁶Sr ratio with the majority of the surrounding igneous rocks; this suggests derivation from different sources with a common initial ratio. Such a relationship could arise by the re‐melting or pronounced fractional crystallisation of magmas which underplated or intruded the lower crust immediately prior to final magma generation. Alternatively, the acidic magmas may have originally formed by partial melting of crustal rocks immediately after a regional isotopic homogenisation. In either case the magmas were derived from originally igneous rocks which were dioritic in chemical composition.     

Sr, C and O isotope systematics in the Pucará basin, central Peru

A combined Sr, O and C isotope study has been carried out in the Pucará basin, central Peru, to compare local isotopic trends of the San Vicente and Shalipayco Zn-Pb Mississippi Valley-type (MVT) deposits with regional geochemical patterns of the sedimentary host basin. Gypsum, limestone and regional replacement dolomite yield ⁸⁷Sr/⁸⁶Sr ratios that fall within or slightly below the published range of seawater ⁸⁷Sr/⁸⁶Sr values for the Lower Jurassic and the Upper Triassic. Our data indicate that the Sr isotopic composition of seawater between the Hettangian and the Toarcian may extend to lower ⁸⁷Sr/⁸⁶Sr ratios than previously published values. An ⁸⁷Sr-enrichment is noted in (1) carbonate rocks from the lowermost part of the Pucará basin, and (2) different carbonate generations at the MVT deposits. This indicates that host rocks at MVT deposits and in the lower-most part of the carbonate sequence interacted with ⁸⁷Srenriched fluids. The fluids acquired their radiogenic nature by interaction with lithologies underlying the carbonate rocks of the Pucará basin. The San Ramón granite, similar Permo-Triassic intrusions and their clastic derivatives in the Mitu Group are likely sources of radiogenic ⁸⁷Sr. The Brazilian shield and its erosion products are an additional potential source of radiogenic ⁸⁷Sr. Volcanic rocks of the Mitu Group are not a significant source for radiogenic ⁸⁷Sr; however, molasse-type sedimentary rocks and volcaniclastic rocks cannot be ruled out as a possible source of radiogenic ⁸⁷Sr. The marked enrichment in ⁸⁷Sr of carbonates toward the lower part of the Pucará Group is accompanied by only a slight decrease in ¹⁸O values and essentially no change in ¹³C values, whereas replacement dolomite and sparry carbonates at the MVT deposits display a coherent trend of progressive ⁸⁷Sr-enrichment, and ¹⁸O- and ¹³C-depletion. The depletion in ¹⁸O in carbonates from the MVT deposits are likely related to a temperature increase, possibly coupled with a ¹⁸O-enrichment of the ore-forming fluids. Progressively lower ¹³C values throughout the paragenetic sequence at the MVT deposits are interpreted as a gradually more important contribution from organically derived carbon. Quantitative calculations show that a single fluid-rock interaction model satisfactorily reproduces the marked ⁸⁷Sr-enrichment and the slight decrease in ¹⁸O values in carbonate rocks from the lower part of the Pucará Group. By contrast, the isotopic covariation trends of the MVT deposits are better reproduced by a model combining fluid mixing and fluid-rock interaction. The modelled ore-bearing fluids have a range of compositions between a hot, saline, radiogenic brine that had interacted with lithologies underlying the Pucará sequence and cooler, dilute brines possibly representing local fluids within the Pucará sequence. The composition of the local fluids varies according to the nature of the lithologies present in the neighborhood of the different MVT deposits. The proportion of the radiogenic fluid in the modelled fluid mixtures interacting with the carbonate host rocks at the MVT deposits decreases as one moves up in the stratigraphic sequence of the Pucará Group.     

Segregation of magmatic fluids and their potential in the mobilization of platinum-group elements in the South Kawishiwi Intrusion,Duluth Complex,Minnesota — Evidence from petrography,apatite geochemistry and coexisting fluid and melt inclusions

Pegmatitic and other felsic rock pockets and dike-like intrusions are abundant in the South Kawishiwi Intrusion of the Duluth Complex, including the basal, Cu–Ni–PGE mineralized units. These occurrences are found as pockets, pods or as veins and contain abundant accessory apatite and quartz. Quartz hosts primary fluid inclusions as well as silicate melt inclusions. Combined microthermometry and Raman spectroscopy helped to determine the bulk composition of primary fluid inclusions that are CO₂-rich (95 mol%) and contain small amounts of H₂O (4.5 mol%), CH₄ (0.4 mol%) and trace N₂, respectively. This combined technique also made it possible to measure total homogenization temperatures of the inclusions (Th_tot = ~ 225 ± 10 °C), otherwise not detectable during microthermometry. Silicate melt inclusions have been quenched to produce homogeneous glasses corresponding to the original melt. Composition of the entrapped melt is granitoid, peraluminous and is very poor in mafic components. We interpret the melt as a product of partial melting of the footwall rocks due to the contact effect of the South Kawishiwi Intrusion. The presence of CO₂ in the vapor bubbles of the quenched melt inclusions and petrographic evidence suggest that the fluid and melt inclusion assemblages are coeval. The composition of the fluid and melt phase implies that the fluid originates from the mafic magma of the South Kawishiwi Intrusion and the fluid and melt phases coexisted as a heterogeneous melt–fluid system until entrapment of the inclusions.Coexistence of primary fluid and melt inclusions makes it possible to calculate a minimum entrapment pressure (~ 1.7 kbar) and thus estimate formation depth (~ 5.8 km) for the inclusions. Chlorine is suggested to behave compatibly in the silicate melt phase in the fluid–melt system represented by the inclusions, indicated by the high (up to 0.3%) Cl-concentrations of the silicate melt and CO₂-rich nature of the fluid.Apatite halogen-contents provide further details on the behavior of Cl. Apatite in pegmatitic pockets often has elevated Cl-concentrations compared to troctolitic rocks, suggesting enrichment of Cl with progressive crystallization. Systematic trends of Cl-loss at some differentiated melt pockets suggest that in some places Cl exsolved into a fluid phase and migrated away from its source. The segregation of Cl from the melt is probably inhibited by the presence of CO₂-rich fluids until the last stages of crystallization, increasing the potential for the development of late-stage saline brines.Platinum-group minerals are often present in microcracks in silicate minerals, in late-stage differentiated sulfide veinlets and in association with chlorapatite, indicating the potential role of Cl-bearing fluids in the final distribution of PGEs.     

Geochronology and Hf isotopes of the bimodal mafic–felsic high heat producing igneous suite from Mt Painter Province,South Australia

The Mt Painter Province of northern South Australia is a site of exceptional suite of Mesoproterozoic high heat producing (HHP) granites and felsic volcanics. These rocks have very high heat production values of > 5 μW m^− 3. The HHP granites, including the Mt Neill, Box Bore, Terrapinna, Wattleowie and Yerila granites, form part of a broadly coeval association of mafic and felsic volcanic rocks that also include the Pepegoona Volcanics, lamprophyres and mafic–intermediate dykes. U–Pb LA-ICPMS zircon dating and Hf-in-zircon isotopic data are used to constrain both the timing and source of these magmatic rocks. U–Pb zircon LA-ICPMS crystallization ages range from ~ 1596 to 1521 Ma and imply a protracted sequence of magmatic events. Initial Hf isotopic compositions of these zircons from both dykes and felsic rocks have overlapping compositional ranges, with ε_Hf values mainly from + 4 to − 2. These Hf values are significantly higher than contemporary crustal values which are likely to have been in the range − 4 to − 20. These data imply that the magmatic suite has both mantle and crustal sources.     

Fluid–rock reactions in the 1.3 Ga siderite carbonatite of the Grønnedal–Íka alkaline complex,Southwest Greenland

Petrogenetic studies of carbonatites are challenging, because carbonatite mineral assemblages and mineral chemistry typically reflect both variable pressure–temperature conditions during crystallization and fluid–rock interaction caused by magmatic–hydrothermal fluids. However, this complexity results in recognizable alteration textures and trace-element signatures in the mineral archive that can be used to reconstruct the magmatic evolution and fluid–rock interaction history of carbonatites. We present new LA–ICP–MS trace-element data for magnetite, calcite, siderite, and ankerite–dolomite–kutnohorite from the iron-rich carbonatites of the 1.3 Ga Grønnedal–Íka alkaline complex, Southwest Greenland. We use these data, in combination with detailed cathodoluminescence imaging, to identify magmatic and secondary geochemical fingerprints preserved in these minerals. The chemical and textural gradients show that a 55 m-thick basaltic dike that crosscuts the carbonatite intrusion has acted as the pathway for hydrothermal fluids enriched in F and CO₂, which have caused mobilization of the LREEs, Nb, Ta, Ba, Sr, Mn, and P. These fluids reacted with and altered the composition of the surrounding carbonatites up to a distance of 40 m from the dike contact and caused formation of magnetite through oxidation of siderite. Our results can be used for discrimination between primary magmatic minerals and later alteration-related assemblages in carbonatites in general, which can lead to a better understanding of how these rare rocks are formed. Our data provide evidence that siderite-bearing ferrocarbonatites can form during late stages of calciocarbonatitic magma evolution.     

Relationship between footwall composition,crustal contamination,and fluid–rock interaction in the Platreef,Bushveld Complex,South Africa

In the northern limb of the 2.06-Ga Bushveld Complex, the Platreef is a platinum group elements (PGE)-, Cu-, and Ni-mineralized zone of pyroxenite that developed at the intrusion margin. From north to south, the footwall rocks of the Platreef change from Archaean granite to dolomite, hornfels, and quartzite. Where the footwall is granite, the Sr-isotope system is more strongly perturbed than where the footwall is Sr-poor dolomite, in which samples show an approximate isochron relationship. The Nd-isotope system for samples of pyroxenite and hanging wall norite shows an approximate isochron relationship with an implied age of 2.17 ± 0.2 Ga and initial Nd-isotope ratio of 0.5095. Assuming an age of 2.06 Ga, the ɛNd values range from −6.2 to −9.6 (ave. −7.8, n = 17) and on average are slightly more negative than the Main Zone of the Bushveld. These data are consistent with local contamination of an already contaminated magma of Main Zone composition. The similarity in isotope composition between the Platreef pyroxenites and the hanging wall norites suggests a common origin. Where the country rock is dolomite, the Platreef has generally higher plagioclase and pyroxene δ ¹⁸O values, and this indicates assimilation of the immediate footwall. Throughout the Platreef, there is considerable petrographic evidence for sub-solidus interaction with fluids, and the Δ _{plagioclase–pyroxene} values range from −2 to +6, which indicates interaction at both high and low temperatures. Whole-rock and mineral δD values suggest that the Platreef interacted with both magmatic and meteoric water, and the lack of disturbance to the Sr-isotope system suggests that fluid–rock interaction took place soon after emplacement. Where the footwall is granite, less negative δD values suggest a greater involvement of meteoric water. Consistently higher values of Δ _{plagioclase–pyroxene} in the Platreef pyroxenites and hanging wall norites in contact with dolomite suggest prolonged interaction with CO₂-rich fluid derived from decarbonation of the footwall rocks. The overprint of post crystallization fluid–rock interaction is the probable cause of the previously documented lack of correlation between PGE and sulfide content on the small scale. The Platreef in contact with dolomite is the focus of the highest PGE grades, and this suggests that dolomite contamination played a role in PGE concentration and deposition, but the exact link remains obscure. It is a possibility that the CO₂ produced by decarbonation of assimilated dolomite enhanced the process of PGE scavenging by sulfide precipitation.     

Age,petrogenesis and metamorphism of the syn-collisional Prøven Igneous Complex,West Greenland

The Paleoproterozoic Prøven Igneous Complex (PIC) in West Greenland extends from ca. 72°15 to 73°10N, approximately 500 km north of the subduction-related intrusive complex in the core of the +1100 km wide, asymmetric collisional Nagssugtoqidian-Rinkian Orogen. A new U-Pb SHRIMP age for the PIC of 1869±9 Ma indicates that it intruded synchronously with the main collisional phase of the orogen into the passive margin side of the collision. Sm-Nd and Lu-Hf isotopic and A-type geochemical signatures are compatible with its derivation from melted Archean lower crustal material contaminated to varying degrees by pelitic sedimentary rocks of the Karrat Group. The timing, petrogenesis and position of the PIC within the orogen support a model of collisionally induced delamination of the mantle lithosphere following initial collision. Upwelling asthenospheric mantle replacing the partially or completely detached mantle lithosphere caused widespread partial melting of lower crust that resulted in the areally extensive (~ 250,000 km²) Cumberland-Prøven intrusive complexes of Baffin Island and West Greenland. Emplacement of the PIC at 1.87 Ga caused a high-temperature low- to medium-pressure metamorphic aureole that contrasts the regional, overprinting higher-pressure amphibolite facies metamorphism. The consequent high-temperature garnet-orthopyroxene-biotite-bearing assemblages occurring within the margin of the intrusion in the aureole are attributed to the intrusion event. Garnet-controlled Sm-Nd and Lu-Hf ages of 1.82–1.80 Ga require efficient diffusion of these elements during orogenic reheating at this time. This age range overlaps the post-collisional, north–south shortening in the Nagssugtoqidian Orogen to the south and serves to confirm the recently proposed genetic link between these two orogens. These new data infer that garnet-controlled isochrons based on the Lu-Hf and Sm-Nd systems cannot date high-grade events in slowly cooled or significantly reheated terrains in rocks possessing other phases that close at low temperatures.     

Origin of the early Permian Wajilitag igneous complex and associated Fe–Ti oxide mineralization in the Tarim large igneous province,NW China

The Wajilitag igneous complex is part of the early Permian Tarim large igneous province in NW China, and is composed of a layered mafic–ultramafic intrusion and associated syenitic plutons. In order to better constrain its origin, and the conditions of associated Fe–Ti oxide mineralization, we carried out an integrated study of mineralogical, geochemical and Sr–Nd–Hf isotopic analyses on selected samples. The Wajilitag igneous rocks have an OIB-like compositional affinity, similar to the coeval mafic dykes in the Bachu region. The layered intrusion consists of olivine clinopyroxenite, coarse-grained clinopyroxenite, fine-grained clinopyroxenite and gabbro from the base upwards. Fe–Ti oxide ores are mainly hosted in fine-grained clinopyroxenite. Forsterite contents in olivines from the olivine clinopyroxenite range from 71 to 76 mol%, indicating crystallization from an evolved magma. Reconstructed composition of the parental magma of the layered intrusion is Fe–Ti-rich, similar to that of the Bachu mafic dykes. Syenite and quartz syenite plutons have ε_Nd(t) values ranging from +1.4 to +2.9, identical to that for the layered intrusion. They may have formed by differentiation of underplated magmas at depth and subsequent fractional crystallization. Magnetites enclosed in olivines and clinopyroxenes have Cr₂O₃ contents higher than those interstitial to silicates in the layered intrusion. This suggests that the Cr-rich magnetite is an early crystallized phase, whereas interstitial magnetite may have accumulated from evolved Fe–Ti-rich melts that percolated through a crystal mush. Low V content in Cr-poor magnetite (<6600 ppm) is consistent with an estimate of oxygen fugacity of FMQ + 1.1 to FMQ + 3.5. We propose that accumulation of Fe–Ti oxides during the late stage of magmatic differentiation may have followed crystallization of Fe–Ti-melt under high fO₂ and a volatile-rich condition.     

Contrasting rock permeability in the aureole of the Ballachulish igneous complex, Scottish Highlands: the influence of surface energy?

The Ballachulish igneous complex in the Scottish Highlands, part of a widespread group of late Caledonian calcalkaline intrusions, was emplaced at a depth of 10 km into Dalradian metasediments resulting in melting of the country rocks near the intrusive contact. The greatest extent of melting occurred in the Leven schist in the 400 m wide so-called Chaotic Zone which experienced infiltration of aqueous fluids from the pluton. In contrast, adjacent to the Chaotic Zone, the feldspar-bearing Appin quartzite underwent significant melting only within a few metres of the intrusion, despite both being in contact with the same fluid source as the Leven schist and having a similar (wet) melting point. The permeability of the Appin quartzite and quartz horizons in the Leven schist to pervasive grain-edge infiltration of aqueous fluids was determined by measuring the equilibrium quartz-H₂O dihedral angle for the P-T conditions of contact metamorphism. Addition of powdered samples of both rock types to the pure quartz-H₂O system results in a linear decrease of the quartz-H₂O dihedral angle with increasing temperature. The rate of this decrease for the Leven schist is greater than that for the Appin quartzite, and the angle decreases below 60° some 30 °C below the wet solidus (670 °C at 0.3 GPa). Charges bearing Appin quartzite had dihedral angles greater than 60° at all temperatures below the wet solidus (690 °C at 0.3 GPa). These results demonstrate that quartz-rich horizons in the Leven schist would have been permeable to infiltration of aqueous fluids close to the solidus, permitting extensive H₂O-fluxed melting to occur. The Appin quartzite would have remained impermeable to grain-edge flow, consistent with the observed differences in the extent of partial melting of the two lithologies. Received: 25 November 1996 / Accepted: 29 October 1997     

K‐Ar dating of Permian and Tertiary igneous activity in the Southeastern Sydney Basin,New South Wales

The southern part of the Sydney Basin of New South Wales is comprised mainly of Permian and Triassic marine to freshwater clastic sedimentary rocks. Within this sequence there are six latite extrusive units, several medium‐sized monzonite intrusions and a large number of small to medium‐sized basic to intermediate intrusions. Thin basaltic flows were extruded onto the Tertiary topographic surface. All of these rocks are relatively undeformed.

Radiometric (K‐Ar) dating has previously been carried out on Mesozoic and Tertiary intrusions and flows of the southwestern portion of the Sydney Basin. However, relatively few Permian, and no post‐Permian, K‐Ar dates have been published for the southeastern portion of the basin. The present investigation provides nine K‐Ar dates from the latter area.

Four extrusive and intrusive units have been confirmed as Permian in age (238 ± 6; 241 ± 4; 245 ± 6; and 251 ± 5 m.y.). Five post‐Permian (on stratigraphic criteria) intrusions yielded Tertiary ages (26.2 ± 3.0; 47.9 ± 2.5; 49.0 ± 4.0; 49.4 ± 2.0; and 58.8 ± 3.5 m.y.). The Permian ages agree with previously published K‐Ar data from the southeastern Sydney Basin, and the Tertiary ages complement and extend the data from the southwestern portion of the basin. However, no Mesozoic K‐Ar dates were obtained from the southeastern Sydney Basin. The Tertiary intrusions may have been emplaced as a result of rifting between Australia and New Zealand, or between Australia and Antarctica, or both.     

Geochemistry and Sm–Nd isotopic systematics of Ediacaran–Ordovician,sedimentary and bimodal igneous rocks in the western Acatlán Complex,southern Mexico: Evidence for rifting on the southern margin of the Rheic Ocean

Ordovician igneous rocks in the western Acatlán Complex (Olinalá area) of southern Mexico include a bimodal igneous suite that intrudes quartzites and gneisses of the Zacango Unit, and all these rocks were polydeformed and metamorphosed in the amphibolite facies during the Devono-Carboniferous. The Ordovician igneous rocks consist of the penecontemporaneous amphibolites, megacrystic granitoids and leucogranite, the latter dated at ca. 464 Ma. Geochemical and Sm–Nd data indicate that the amphibolites have a differentiated tholeiitic signature, and that its mafic protoliths formed in an extensional setting transitional between within-plate and ocean floor. The amphibolites are variably contaminated by a Mesoproterozoic crustal source, inferred to be the Oaxacan basement exposed in the adjacent terrane. The most primitive samples have εNdt (t = 465 Ma) values significantly below that of the contemporary depleted mantle and were probably derived from the sub-continental lithospheric mantle. The megacrystic granites were most probably derived by partial melting of an arc crustal source (similar to the Oaxacan Complex) and triggered by the ascent of mafic magma from the lithospheric mantle. Sm–Nd isotopic signatures suggest that metasedimentary rocks from Zacango Unit were derived from adjacent Oaxacan Complex. Trace elements relationships (e.g. La/Th vs. Hf) and REE patterns suggest provenance in felsic-intermediate igneous rocks with a calc-alkaline signature. The Ordovician bimodal magmatism is inferred to have resulted from rifting on the southern flank of the Rheic Ocean and is an expression of a major rifting event that occurred along much of the northern Gondwanan margin in the Ordovician.     

Zircon geochronology of the Koraput alkaline complex: Insights from combined geochemical and U–Pb–Hf isotope analyses,and implications for the timing of alkaline magmatism in the Eastern Ghats Belt,India

Zircon formation and modification during magmatic crystallization and high-grade metamorphism are explored using TIMS and LA-ICP-MS U–Pb geochronology, Lu–Hf isotope chemistry, trace element analysis and textural clues on zircons from the Koraput alkaline intrusion, Eastern Ghats Belt (EGB), India. The zircon host-rock is a granulite-facies nepheline syenite gneiss with an exceptionally low Zr concentration, prohibiting early magmatic Zr saturation. With zircon formation occurring at a late stage of advanced magmatic cooling, significant amounts of Zr were incorporated into biotite, nearly the only other Zr-bearing phase in the nepheline syenite gneisses. Investigated zircons experienced a multi-stage history of magmatic and metamorphic zircon growth with repeated solid-state recrystallization and partial dissolution–precipitation. These processes are recorded by complex patterns of internal zircon structures and a wide range of apparently concordant U–Pb ages between 869 ± 7 Ma and 690 ± 1 Ma. The oldest ages are interpreted to represent the timing of the emplacement of the Koraput alkaline complex, which significantly postdates the intrusion ages of most of the alkaline intrusion in the western EGB. However, Hf model ages of TDM = 1.5 to 1.0 Ga suggest an earlier separation of the nepheline syenite magma from its depleted mantle source, overlapping with the widespread Mesoproterozoic, rift-related alkaline magmatism in the EGB. Zircons yielding ages younger than 860 Ma have most probably experienced partial resetting of their U–Pb ages during repeated and variable recrystallization events. Consistent youngest LA-ICP-MS and CA-TIMS U–Pb ages of 700–690 Ma reflect a final pulse of high-grade metamorphism in the Koraput area and underline the recurrence of considerable orogenic activity in the western EGB during the Neoproterozoic. Within the nepheline syenite gneisses this final high-grade metamorphic event caused biotite breakdown, releasing sufficient Zr for local saturation and new subsolidus zircon growth along the biotite grain boundaries.     

Adsorption behaviors of Cd^2＋ on Fe2O3/MnO2 and the effects of coexisting ions under alkaline conditions

This study describes the adsorption features of cadmium on Fe2O3 and MnO2 in alkaline saline conditions. The adsorption reached equilibrium in 6 hours under alkaline conditions. The absorption of cadmium on Fe2O3 and MnO2 was consistent with Freundlich absorption isotherms, and the corresponding adsorption capacities were 16.3 and 16.7 mg·g-1, respectively. Moreover, the adsorption quantity of cadmium on Fe2O3 and MnO2 rose with increasing pH from acidic to neutral, and reached the maximum at pH= 9. The coexisting chlorides reduced the adsorption capacity of Fe2O3 and MnO2. The influence intensities of different cations follow the order of CaCl2>>KCl>NaCl. However, the influence of sodium salts on the capacities of Fe2O3 and MnO2 to adsorb cadmium appeared more complicated: the relatively low concentrations of sodium salts could reduce the adsorption capacity; with increasing concentrations of sodium salts, e.g. NaCl and NaNO3. The adsorption capacity decreased continually. Moreover, due to the competition adsorption and precipitation effects, the adsorption capabilities of Na2CO3, NaH2PO4 and Na2HSO4 could also be reduced and cadmium concentrations in the solution were reduced as well.     

Hydrothermal alteration and Cu–Ni–PGE mobilization in the charnockitic rocks of the footwall of the South Kawishiwi intrusion,Duluth Complex,USA

In the Neoarchean (~ 2.7 Ga) contact metamorphosed charnockitic footwall of the Mesoproterosoic (1.1 Ga) South Kawishiwi intrusion of the Duluth Complex, the primary metamorphic mineral assemblage and Cu–Ni–PGE sulfide mineralization is overprinted by an actinolite + chlorite + cummingtonite + prehnite + pumpellyite + quartz + calcite hydrothermal mineral assemblage along 2–3 cm thick veins. In calcite, hosted by the hydrothermal alteration zones and in a single recrystallized quartz porphyroblast, four different fluid inclusion assemblages are documented; the composition of these fluid inclusions provide p–T conditions of the fluid flow, and helps to define the origin of the fluids and evaluate their role in the remobilization and reprecipitation of the primary metamorphic sulfide assemblage.Pure CO₂ fluid inclusions were found as early inclusions in recrystallized quartz porphyroblast. These inclusions may have been trapped during the recrystallization of the quartz during the contact metamorphism of the footwall charnockite in the footwall of the SKI. The estimated trapping pressure (1.6–2.0 kbar) and temperature (810–920 °C) conditions correspond to estimates based on felsic veins in the basal zones of the South Kawishiwi intrusion.Fluid inclusion assemblages with CO₂–H₂O–NaCl and CH₄–N₂–H₂O–NaCl compositions found in this study along healed microfractures in the recrystallized quartz porphyroblast establish the heterogeneous state of the fluids during entrapment. The estimated trapping pressure and temperature conditions (240–650 bar and 120–150 °C for CO₂–H₂O–NaCl inclusions and 315–360 bar and 145–165 °C for CH₄–N₂–H₂O–NaCl inclusions) are significantly lower than the p–T conditions (> 700 °C and 1.6–2 kbar) during the contact metamorphism, indicating that this fluid flow might not be related to the cooling of the Duluth Complex and its contact aureole. The presence of chalcopyrite inclusions in these fluid inclusions and in the trails of these fluid inclusion assemblages confirms that at least on local scale these fluids played a role in base metal remobilization. No evidences have been observed for PGE remobilization and transport in the samples. The source of the carbonic phase in the carbonic assemblages (CO₂; CH₄) could be the graphite, present in the metasedimentary hornfelsed inclusions in the basal zones of the South Kawishiwi intrusion.The hydrothermal veins in the charnockite can be characterized by an actinolite + cummingtonite + chlorite + prehnite + pumpellyite + calcite (I–II) + quartz mineral assemblage. Chlorite thermometry yields temperatures around 276–308 °C during the earliest phase of the fluid flow. In the late calcite (II) phase, high salinity (21.6–28.8 NaCl + CaCl₂ equiv. wt.%), low temperature (90–160 °C), primary aqueous inclusions were found. Chalcopyrite (± sphalerite ± millerite), replacing and intersecting the early hydrothermal phases, are associated to the late calcite (II) phase. The composition of the formational fluids in the Canadian Shield is comparable with the composition of the studied fluid inclusions. This suggests that the composition of the fluids did not change in the past 2 Ga and base metal remobilization by formational fluids could have taken place any time after the formation of the South Kawishiwi intrusion.Sulfur isotope studies carried out on the primary metamorphic (δ³⁴S = 7.4–8.9‰) and the hydrothermal sulfide mineral assemblage (δ³⁴S = 5.5–5.7‰) proves, that during the hydrothermal fluid flow the primary metamorphic ores were remobilized.     

Carbon isotope systematics of the Cambrian–Vendian aquifer system in the northern Baltic Basin: Implications to the age and evolution of groundwater

Groundwater in the Cambrian–Vendian aquifer system has a strongly depleted stable isotope composition (δ¹⁸O values of about −22‰) and a low radiocarbon concentration, which suggests that the water is of glacial origin from the last Ice Age. The aim of this paper was to elucidate the timing of infiltration of glacial waters and to understand the geochemical evolution of this groundwater. The composition of the dissolved inorganic C (DIC) in Cambrian–Vendian groundwater is influenced by complex reactions and isotope exchange processes between water, organic materials and rock matrix. The δ¹³C composition of dissolved inorganic C in Cambrian–Vendian water also indicates a bacterial modification of the isotope system. The corrected radiocarbon ages of groundwater are between 14,000 and 27,000 radiocarbon years, which is coeval with the advance of the Weichselian Glacier in the area.